本文選題：非晶合金 + 玻璃形成能力��； 參考：《南京航空航天大學(xué)》2016年博士論文

【摘要】：非晶合金具有長(zhǎng)程無(wú)序短程有序的結(jié)構(gòu)特點(diǎn),因此其擁有許多比晶態(tài)合金更加優(yōu)異的宏觀性能,但也使其微觀結(jié)構(gòu)的研究充滿挑戰(zhàn)。而非晶合金微觀結(jié)構(gòu)的研究對(duì)理解其宏觀性能具有重要的意義。非晶合金的玻璃形成能力(GFA)對(duì)于成分的改變十分敏感,改變一點(diǎn)成分配比或者微量摻雜都會(huì)導(dǎo)致GFA的顯著變化,而且由于影響GFA的微觀結(jié)構(gòu)因素目前尚不清楚,因此很難從根本上解決GFA對(duì)成分的高度依賴性。為了能夠開發(fā)具有高GFA的非晶合金,澄清微觀結(jié)構(gòu)與GFA之間的關(guān)聯(lián)性就顯得尤為重要。在本工作中,我們選擇Zr基合金體系作為研究對(duì)象,尋找影響非晶合金GFA的微觀結(jié)構(gòu)層面的因素與機(jī)制�；谕捷椛鋁射線衍射實(shí)驗(yàn)和X射線吸收實(shí)驗(yàn),結(jié)合理論模擬計(jì)算研究了Zr Cu二元合金體系的微觀結(jié)構(gòu)。在選取的五種成分中,不同樣品之間的微觀原子團(tuán)簇的化學(xué)或幾何特征沒有顯著區(qū)別,但是可以探測(cè)到在GFA最佳點(diǎn)Cu64Zr36成分處的非晶相中Zr原子(溶質(zhì)原子)為中心團(tuán)簇具有更高的原子堆積效率,并且相對(duì)于以溶劑原子為中心團(tuán)簇,以溶質(zhì)原子為中心團(tuán)簇為更加致密的結(jié)構(gòu)單元。通過(guò)對(duì)團(tuán)簇的規(guī)則度分析發(fā)現(xiàn)GFA最佳點(diǎn)Cu64Zr36成分處的非晶相中的團(tuán)簇具有相對(duì)較高規(guī)則度。以上結(jié)構(gòu)特征使得非晶結(jié)構(gòu)更為穩(wěn)定,因此對(duì)比其他成分相近的非晶相,Cu64Zr36具有最高GFA。利用同步輻射X射線衍射實(shí)驗(yàn)和同步輻射X射線吸收實(shí)驗(yàn)并結(jié)合RMC模擬、Voronoi分形分析等方法系統(tǒng)研究了Zr50Cu50二元非晶合金與Zr48Cu45Al7三元非晶合金的微觀結(jié)構(gòu)特征。發(fā)現(xiàn)Al原子與其近鄰的Zr和Cu原子之間存在強(qiáng)的雜化相互作用,導(dǎo)致了Al-Zr、Al-Cu原子對(duì)間距的縮短,進(jìn)而引起Zr48Cu45Al7微觀團(tuán)簇體積的收縮,使得非晶合金局部結(jié)構(gòu)在團(tuán)簇尺度存在致密堆積,導(dǎo)致Zr48Cu45Al7 GFA顯著增強(qiáng)。利用同步輻射技術(shù)與理論模擬方法從結(jié)構(gòu)層面揭示了在Zr Cu Al大塊非晶合金的基礎(chǔ)上分別進(jìn)行Gd、Ag和Fe元素?fù)诫s從而導(dǎo)致其GFA顯著提高的原因。在Zr Cu Al Gd四元體系中,Zr45Cu46Al7Gd2樣品中由于添加2%含量Gd元素,使得以溶質(zhì)原子為中心團(tuán)簇的數(shù)量與穩(wěn)定性都有所增加,并且導(dǎo)致在原子和團(tuán)簇層面其結(jié)構(gòu)具有相對(duì)更高的堆積效率,可以顯著增強(qiáng)其GFA。但在Zr42Cu46Al7Gd5樣品中,由于出現(xiàn)Al-Gd(溶質(zhì)原子-溶質(zhì)原子)直接鍵合,原子結(jié)構(gòu)的堆積效率降低,導(dǎo)致GFA的降低;在Zr Cu Al Ag四元體系中,發(fā)現(xiàn)Ag摻雜于Zr Cu Al體系之后,不僅增加了Al原子周圍的類二十面體局域結(jié)構(gòu)的含量,而且使得Zr和Cu原子為中心的團(tuán)簇更規(guī)則。這些結(jié)構(gòu)因素使得玻璃態(tài)結(jié)構(gòu)更加穩(wěn)定,顯著增強(qiáng)了合金體系的GFA。然而,當(dāng)加入過(guò)量Ag時(shí),以上結(jié)構(gòu)因素起到的作用被削弱,導(dǎo)致了GFA的降低;在Zr Cu Al Fe四元體系中,發(fā)現(xiàn)Zr60Cu25Fe5Al10樣品中含有大量具有高五次對(duì)稱性特征的結(jié)構(gòu),其團(tuán)簇也更規(guī)則,原子堆積效率更高,在異種原子之間存在強(qiáng)的相互作用。以上結(jié)構(gòu)特點(diǎn)導(dǎo)致Zr60Cu25Fe5Al10具有更高的GFA。而當(dāng)Fe摻入過(guò)量時(shí),以上結(jié)構(gòu)特點(diǎn)被削弱,導(dǎo)致GFA的降低。選用大塊非晶合金成分Zr48Cu45Al7在不同冷卻速率下得到棒狀(低冷卻速率)和條帶(高冷卻速率)樣品,利用同步輻射技術(shù)結(jié)合模擬計(jì)算研究了兩種樣品的微觀結(jié)構(gòu)。在改變冷卻速率的情況下,非晶合金中的以Zr原子為中心的局域結(jié)構(gòu)沒有發(fā)生明顯的變化,而Al原子和Cu原子周圍的局域結(jié)構(gòu)發(fā)生了較大的變化,主要表現(xiàn)為在棒狀樣品的Cu原子周圍的近鄰配位數(shù)小于條帶樣品,而Al原子周圍的近鄰配位數(shù)則大于條帶樣品;棒狀樣品的Al原子周圍的近鄰原子更趨向于分布在相對(duì)局域化的位置。棒狀樣品中Al和Cu原子為中心的團(tuán)簇的原子堆積效率高于條帶樣品,特別是以Al原子為中心團(tuán)簇的原子堆積效率的差別最大,達(dá)到1.6%;相對(duì)于條帶樣品,棒狀樣品中Al原子周圍的局域結(jié)構(gòu)更規(guī)則。而Al原子因?yàn)槠錆舛容^低,可被視為溶質(zhì)原子,所以可以推斷溶質(zhì)原子為中心的局域結(jié)構(gòu)比溶劑原子為中心的局域結(jié)構(gòu)對(duì)冷卻速率更為敏感。
[Abstract]:Amorphous alloys have the structural characteristics of long range disorder and short range order, so they have a lot of better macroscopic properties than crystalline alloys, but it also challenges the study of their microstructure, and the study of the microstructure of amorphous alloys is of great significance for understanding its macroscopic properties. The glass forming ability (GFA) of amorphous alloys is of great importance. The change of the fraction is very sensitive. Changing a bit of composition or trace doping will lead to significant changes in the GFA, and it is difficult to fundamentally solve the high dependence of the GFA on the composition because of the microstructural factors affecting the GFA. In order to develop the amorphous alloy with high GFA, the microstructure and GFA can be clarified. In this work, we choose the Zr based alloy system as the research object and find the factors and mechanisms to influence the microstructure of amorphous alloy GFA. Based on the X ray diffraction experiment of synchrotron radiation and the X ray absorption experiment, the microstructure of the Zr Cu two element alloy system is studied and studied in theory. In the selected five components, there is no significant difference in the chemical or geometric characteristics of the microscopic atomic clusters between different samples, but it can be detected that the Zr atom (solute atom) of the Zr atom (solute atom) at the amorphous phase of the Cu64Zr36 component at the best point of the GFA has a higher atomic accumulation efficiency, and is soluble in relation to the solvent atom as the central cluster. The mass atom is the denser structural unit of the central cluster. By the analysis of the regularity of the cluster, it is found that the clusters in the amorphous phase of the GFA best point Cu64Zr36 have relatively high regularity. The above structural features make the amorphous structure more stable, so Cu64Zr36 has the highest GFA. utilization compared to the other amorphous phase. Synchrotron radiation X ray diffraction (synchrotron radiation) and synchrotron radiation X ray absorption experiments, combined with RMC simulation and Voronoi fractal analysis, have been used to systematically study the microstructure characteristics of Zr50Cu50 two element amorphous alloy and Zr48Cu45Al7 three element amorphous alloy. It is found that there is a strong hybrid interaction between Al atoms and their adjacent Zr and Cu atoms, resulting in Al-Z. The shortening of the space between R and Al-Cu atoms causes the contraction of the size of the Zr48Cu45Al7 cluster, which makes the local structure of the amorphous alloy dense accumulation in the cluster scale and leads to the significant enhancement of the Zr48Cu45Al7 GFA. Using the synchrotron radiation technique and the theoretical simulation method, the amorphous alloy of Zr Cu Al is revealed on the basis of the structure layer. The doping of Gd, Ag and Fe leads to the significant improvement of its GFA. In the Zr Cu Al Gd four element system, the number and stability of the solute atoms as the central cluster increases with the addition of 2% Gd elements in the Zr45Cu46Al7Gd2 sample, and the structure has a relatively higher accumulation effect at the atomic and cluster level. Rate can significantly enhance its GFA., but in Zr42Cu46Al7Gd5 samples, due to the direct bonding of Al-Gd (solute atom), the accumulation efficiency of the atomic structure is reduced and the GFA is reduced. In the Zr Cu Al Ag four element system, it is found that Ag doping in Zr Cu Al system not only increases the local structure of the class twenty surface around the atom, but also the Zr Cu Al system. Content, and make Zr and Cu atoms centered clusters more regular. These structural factors make the glass structure more stable and significantly enhance the GFA. of the alloy system, however, when excess Ag is added, the role of the above structural factors is weakened, resulting in the decrease of GFA; in the Zr Cu Al Fe four element system, the discovery of Zr60Cu25Fe5Al10 samples is found. It contains a large number of structures with high five times symmetry, and its clusters are more regular, with higher atomic accumulation efficiency and strong interaction between dissimilar atoms. The above structural characteristics cause Zr60Cu25Fe5Al10 to have a higher GFA. and when Fe is overdoped, the above structural characteristics are weakened, resulting in the reduction of GFA. The microstructures of the two samples were studied by the synchrotron radiation technique combined with the synchrotron radiation technique at different cooling rates. In the case of changing the cooling rate, the local structure of the Zr precursor in the amorphous alloy has not changed significantly. The local structure around the Al atom and the Cu atom has been greatly changed, which mainly shows that the adjacent neighbour coordination number around the Cu atom in the bar like sample is smaller than the strip sample, while the adjacent neighbour coordination number around the Al atom is larger than the strip sample, and the adjacent adjacent atoms around the Al atoms of the bar like samples tend to be distributed in the relative localization. The accumulation efficiency of the clusters of Al and Cu atoms centered in the rod like samples is higher than that of the strip, especially the accumulation efficiency of the atomic clusters with Al atoms is the largest, reaching 1.6%. Compared with the strip samples, the local structure around the Al atom in the bar like samples is more regular. And the Al atom can be considered as a solute because of its low concentration. Therefore, it can be deduced that the local structure of solute atom centered is more sensitive to the cooling rate than the local structure centered on solvent atoms.
【學(xué)位授予單位】：南京航空航天大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TG139.8

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